Acidity-Basicity
Data (pKa Values) in
Nonaqueous Solvents
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The highlighted papers contain large amounts of
data (acids – red, bases – blue, both acids and bases –
purple)
Publication
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Data
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Medium
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Method
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Description
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Available files
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J. Phys. Org. Chem. 2013, 26, 162-170.
|
pKa values, gas-phase
acidity values |
Acetonitrile, Water, 1,2-Dichloroethane, Gas
phase |
UV-Vis Spectrophotometry, FT-ICR, quantum
chemistry (DFT B3LYP 6-311+G**), COSMO-RS, SMD |
Acidities
(pKa) of a number of
different acids including the well-known
superacids trifluoromethanesulfonic (triflic) acid, HBr, HI,
bis-trifylimide (Tf2NH), etc as well as weaker acids (HCl, acetic
acid, phenol) etc are presented in media of different physical and chemical
nature: water, acetonitrile (AN, MeCN), 1,2-dichloroethane (DCE) and the gas
phase, with special emphasis on strong acids. Dependence of the acidity
trends on moving from water to the gas phase on the nature of the acidity
centre and the molecular structure are analyzed. The acidity orders are
different in water, AN, DCE and the gas phase. It is demonstrated that the
decisive factor for behavior of the acids when transferring between different
media is the extent of charge delocalization in the anion and that the
recently introduced WAPS parameter in spite of its simplicity enables
interpretation of the trends in the majority of cases. |
pKa values (scheme) in water, acetonitrile, dichloroethane
and gas-phase acidities (PDF) Table of pKa
values in water, acetonitrile, 1,2-dichloroethane and gas phase
(PDF) |
Eur. J. Org. Chem. 2012, 2167-2172
|
pKa values |
Acetonitrile |
UV-Vis Spectrophotometry |
Basicity
(pKa values) of a number
of phosphanes (phosphines) – both monophosphanes
(monophosphines) and diphosphanes
(diphosphines, common ligands in catalysts) – and amines in MeCN.
Compounds: triphenylphosphine, trimethylphosphine, bis-diphenylphosphinoethane,
bis-diphenylphosphinopropane, BINAP, BIPHEP, etc. The possibility of intramolecular hydrogen
bond formation in protonated diphosphines is assessed. |
|
"Design and acidity measurements
of superacidic molecules", presented at ESOR XIII Tartu, on 14.09.2011
|
pKa values, gas-phase
acidity values |
MeCN, 1,2-dichloroethane, gas phase |
Spectrophotometry, FT-ICR, quantum chemistry
(DFT B3LYP 6-311+G**) |
An
overview was given about the principles of design and acidity measurement of superacids (superacidic molecules),
illustrated by numerous acidity data. |
Full talk (PDF) |
Chem. Eng. J. 2011, 171, 794-800
|
pKa values |
MeCN |
COSMO-RS (and some experimental from
different sources) |
pKa values of different CO2-binding
organic liquids (CO2BOLs) have been calculated (using COSMO-RS) or
collected from the literature and related to the performance of the CO2BOLs
in CO2 capture. |
|
J. Org. Chem. 2011, 76, 391-395
|
pKa values |
1,2-dichloroethane (also acetonitrile) |
Spectrophotometric |
Relative
acidities of 64 strong acids (some
of them superacids) in 1,2-dichloroethane and 54
strong acids in acetonitrile. Included are numerous sulfonimides, cyanocarbon
acids and well-known mineral acids, such as HCl, HBr, HI, H2SO4,
HNO3, HBF4, CF3SO3H, FSO3H,
HClO4, (CF3SO2)2NH (Tf2NH)
and (C2F5SO2)2NH. Contains some pKa values of acid
catalysts. |
Table
of pKa values in
1,2-dichloroethane (with estimated values in MeCN) (PDF) |
J. Phys. Chem. A 2010, 114, 10694-10699
|
Gas-phase
basicity values |
Gas phase |
FT-ICR, quantum chemistry (W1, G2) |
Gas-phase
basicity values for weak bases: CS2,
water, FCN, C2H4, CF3CN, (CF3)2CHOH,
F2NH, CF3CHO, C6F6, CH3Cl,
(CF3)3COH, CF3COCl, (CN)2,
FSO2Cl, SO2, (CF3)2CO, COS, F2CO,
CF3CCH, (CF3)2O and SO2F2.
The assigned values have been obtained by combining and critically evaluating
data from multiple experimental and theoretical sources and are thus expected
to be highly reliable. |
|
Angew. Chem. Int. Ed. 2010, 49, 6885-6888.
|
Absolute
acidity values |
Acetonitrile, DMSO, water, benzene, etc. |
Computations using the rCCC model |
On the
basis of the absolute chemical potential of the proton, a unified absolute pH scale is
introduced that is universally applicable in the gas phase, in solution, and
in the solid state. With this scale it is possible to directly compare
acidities in different media and to give a thermodynamically meaningful
definition of superacidity. |
Table
of available acidity ranges in selected solvents (PDF) |
J. Phys. Chem. A 2009, 113, 8421-8424
|
pKa values and Gas-phase
acidity values |
Acetonitrile, gas phase |
Spectrophotometric, FT-ICR, G3(MP2), DFT
B3LYP 6-311+G** |
Gas-phase
acidity and pKa values in
MeCN for a number of aromatic
sulfonimides, fluorinated aliphatic sulfonimides, including Tf2NH
and (C2F5SO2)2NH, and some other
acids. The work presents revision of the gas-phase acidity (GA) scale from
(CF3CO)2NH to (C2F5SO2)2NH,
i.e. about a 24 kcal mol-1 range of gas phase acidities and ends
the controversy between experiment and computations in this acidity range. |
Table of experimental and computational gas-phase
acidities and pKa values
in acetonitrile (PDF) |
J. Comp. Chem. 2009, 30, 799-810
|
pKa values |
Acetonitrile |
Spectrophotometric |
Experimental
pKa
values of more than 200 neutral acids in acetonitrile (from our group and
from other authors) ranging from pKa
3.6 to 29. Acids: alcohols, carboxylic acids (acetic acid, trifluoroacetic acid,
benzoic acid, different diacids, e.g. phthalic acid, oxalic acid, succinic
acid), phenols (nitrophenols, chlorophenols, 2,4-dinitrophenol,
2,4,6-Trinitrophenol (picric acid), etc), sulfonic acids (para-toluene
sulfonic acid, substituted benzenesulfonic acids), anilines, sulfonamides,
phenylmalononitriles, diphenylacetonitriles, strong acids (perchloric acid,
fluorosulfuric acid, methanesulfonic acid, 4-toluenesulfonic acid) acid
catalysts, etc. The work
aims at computational (COSMO-RS) estimation of MeCN pKa values and the experimental values of our group are
used as fit data set and values from other authors as test data set. |
Tables of pKa values (PDF) |
J. Org. Chem. 2008, 73, 2607-2620
|
pKa values and Gas-phase
acidity values |
Acetonitrile, DMSO, Water, gas phase |
Spectrophotometric, FT-ICR, DFT B3LYP
6-311+G** |
Gas-phase
acidity and pKa values
for a number of poly-CF3-substituted aromatic compounds. Included
are (CF3)5Phenol, (CF3)5Aniline,
(CF3)5Toluene and (CF3)5Phenylmalononitrile. |
Table of experimental pKa values and Gas-phase acidities (PDF) |
Chem. Eur. J. 2007, 13,
7631-7643
|
pKa values and Gas-phase
basicity values |
Acetonitrile, Tetrahydrofuran, gas phase |
Spectrophotometric, FT-ICR, DFT B3LYP
6-311+G** |
Gas-phase
basicity and pKa values for a number of diamines and related
monoamines. Included are different substituted diamines: 1,3-propanediamine
(1,3-diaminopropane) and its derivatives, tetramethylated 1,2-ethanediamine
(1,2-diaminoethane) and 1,4-butanediamine (1,4-diaminobutane), piperidine,
piperazine, bispidine, dimethylbispidine. |
Schemes of base structures, table of pKa and gas-phase basicity
values (PDF) |
"Brønsted Acidity of
Neutral and Cationic Acids in Nonaqueous Solvents: Recent Developments",
(INOR 1036) presented at the ACS Spring meeting Mar 27, 2007,
Chicago
|
pKa
values |
Acetonitrile, Heptane, 1,2-Dichloroethane,
THF, gas phase |
spectrophotometric, FT-ICR |
This is a
poster summarizing the Brønsted acidity and basicity data gathered by our
group during the recent years. |
Full poster (PDF) |
J. Phys. Chem. A 2007, 111,
1245-1250
|
Gas-phase
basicity values |
gas phase |
FT-ICR, spectrophotometric |
Gas-phase basicity for 30 superbases: phosphazene superbases: P2-phosphazenes
(EtP2, PhP2, …), P1-phosphazenes (t-BuP1, EtP1,
MeP1, …), BEMP superbase; MTBD, ETBD, ITBD, Verkade's
superbases |
Scheme of base structures, table
gas-phase basicity values (PDF) |
Anal.
Chim. Acta. 2006, 566, 290-303
|
Uncertainty |
MeCN |
Spectrophotometric |
Uncertainty
estimation in measurement of pKa
values in nonaqueous media (solvents) using two different approaches. |
Table of pKa
values, experimental measurement results and uncertainty values (PDF) |
J. Org. Chem. 2006, 71,
2829-2838
|
pKa
values |
Acetonitrile |
Spectrophotometric |
pKa values of 93
neutral acids in
acetonitrile ranging from pKa
3.7 to 28.1. Acids: alcohols, carboxylic acids (acetic acid, benzoic acid), phenols
(2,4-dinitrophenol, picric acid, etc), sulfonic acids (para-toluene sulfonic
acid, substituted benzenesulfonic acids), anilines, sulfonamides,
phenylmalononitriles, diphenylacetonitriles, etc. Titrants: trifluoromethanesulfonic acid (triflic acid) and
phosphazenes t-BuP1(pyrr)
and EtP2(dma) |
Table of pKa
values and experimental measurement results (PDF) |
J. Org. Chem. 2006, 71, 7155-7164
|
pKa
values |
Acetonitrile |
Spectrophotometric |
Acetonitrile
pKa values of 10
substituted bispidine bases. |
Table of bispidine structures and table
of pKa measurement
results (PDF) |
J. Am. Chem. Soc. 2005, 127, 17656-17666
|
pKa
values GPB, PA |
Tetrahydrofuran Calculation |
Spectrophotometric DFT B3LYP 6-311+G** |
pKa values of phosphazene bases and
Brønsted basicity calculations of guanidinophosphazenes and related bases.
Several of them qualify as superbases. |
|
J. Org. Chem. 2005, 70,
1019-1028
|
pKa
values |
Acetonitrile |
Spectrophotometric |
pKa values of 89
neutral bases in
acetonitrile ranging from 4-Cl-2-NO2-Aniline (pKa = 3.80) to 4-MeO-C6H4-N=P(N=P(Nme2)3)(Nme2)
(pKa = 31.99). Among the bases are: phosphazene superbases, DBU, TBD, MTBD superbase,
proton sponge, triethylamine, pyrrolidine (and other substituted amines)
pyridine and substituted pyridines (DMAP, etc), aniline and substituted
anilines. |
Table of pKa values and experimental measurement results
(PDF) |
J. Org. Chem. 2003,
68, 9988-9993
|
pKip,
pKa values GPB |
Tetrahydrofuran |
Spectrophotometric FT-ICR spectrometric |
pKa and pKip values of 31 bases in tetrahydrofuran ranging from
4‑CF3-C6H4-P1(pyrr) (pKa = 14,6) to 2‑Cl‑C6H4‑P4(pyrr)
(pKa = 26,6). Gas-Phase basicities of
10 bases. |
Tables of pKip, pKa and GBP values and experimental
measurements results (PDF) |
J. Org. Chem. 2003,
68, 7795-7799
|
pKip
values |
Heptane |
Spectrophotometric |
Relative
pKip values of 21 weak
acids in heptane. |
Table of pKip
values and experimental measurements results (PDF) |
J. Chem. Soc., Perkin Trans. 2. 2002, 1950-1955
|
pKa
values |
Acetonitrile |
Spectrophotometric |
Acetonitrile
pKa values of some
amides and imidines of benzoic acid. The acidifying effect of the substituent
=NSO2CF3. |
|
Inorg.
Chim. Acta. 2002, 340, 87-96.
|
pKa
table |
Acetonitrile |
Spectrophotometric |
pKa values for neutral and cationic
bases in MeCN. Used a different calculation method to get also pKa values of cationic
bases. |
|
J. Org. Chem. 2002,
67, 1873-1881
|
pKip,
pKa values |
Tetrahydrofuran |
Spectrophotometric |
pKa and pKip values of 45 bases in tetrahydrofuran ranging from
2-MeO-Pyridine (pKa = 2,6) to EtP1(pyrr)
(pKa = 21,5). Among the
bases are: various phosphazene superbases (incl. several Schwesinger's
phosphazenes), DBU, TBD, TMG, pyridine, aniline, etc. |
|
J. Chem. Soc., Perkin Trans. 2. 2001, 229-232
|
pKa
values GPA |
Dimethyl sulfoxide |
Potentiometric FT-ICR spectrometric |
The
acidifying effect of the substituent =NSO2CF3 on the acidity of derivatives
of benzenesulfonamide and toluene-p-sulfonamide in the gas phase and in
dimethyl sulfoxide (DMSO) |
|
J. Org. Chem. 2000,
65, 6202-6208
|
pKa
table |
MeCN |
Spectrophotometric |
pKa values of 29 bases in
acetonitrile ranging from Pyridine (pKa
= 12,33) to DBU (pKa =
24,13) |
Table of pKa values and experimental measurement results
(PDF) |
J. Chem. Soc., Perkin Trans. 2. 2000, 1125-1133
|
pKa
values GPA-s |
Dimethyl sulfoxide |
Potentiometric FT-ICR spectrometric |
Comparison
of Brønsted acidities of neutral CH-acids in gas phase and dimethyl
sulfoxide. A voluminous acidity table in DMSO and gas phase (Fluorene,
indene, cyclopentadiene, fluoradene, …). |
Acidity table (table of pKa values) in dimethyl sulfoxide and GPB (PDF) |
J. Org. Chem. 1998,
63, 7868-7874
|
pKa
table |
Acetonitrile |
Spectrophotometric |
pKa values (dissociation constants)
of 36 acids in acetonitrile ranging from 4-Cl-C6H4-SO(=NTf)-NH-SO2-C6H4-4-NO2
(pK = 3,75) to 2,4-dinitrophenol (pK = 16,66) |
Table of dissociation constants (pKa values) in acetonitrile and
experimental measurement results (PDF) |
J. Org. Chem. 1997,
62, 8479-8483
|
pKip
values |
Heptane |
Spectrophotometric |
Relative
pKip (acidity constants)
values of 6 weak acids in heptane. |
Table of pKip
values and experimental measurements results (PDF) |
Comments
|
Should
you have any questions regarding the data, the used experimental, data
treatment or computational methods, etc, please do not hesitate to contact
Ivo Leito (e-mail: ivo.leito |
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Chair of Analytical chemistry |
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University of Tartu 2012 |
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Last edited: Saturday, 02-Feb-2013 21:07:18 EET